CN111574330A - Separation method of crude phenol and organic amine mixture - Google Patents
Separation method of crude phenol and organic amine mixture Download PDFInfo
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- CN111574330A CN111574330A CN202010555793.9A CN202010555793A CN111574330A CN 111574330 A CN111574330 A CN 111574330A CN 202010555793 A CN202010555793 A CN 202010555793A CN 111574330 A CN111574330 A CN 111574330A
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- water
- phenol
- organic amine
- organic solvent
- organic
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 366
- 150000001412 amines Chemical class 0.000 title claims abstract description 287
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 238000000926 separation method Methods 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 306
- 239000003960 organic solvent Substances 0.000 claims abstract description 238
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 36
- 230000020477 pH reduction Effects 0.000 claims abstract description 28
- 238000000605 extraction Methods 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 239000002535 acidifier Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 29
- 239000012535 impurity Substances 0.000 claims description 23
- -1 alcohol amine Chemical class 0.000 claims description 14
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000003321 amplification Effects 0.000 abstract description 4
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 178
- 238000003756 stirring Methods 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 30
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 24
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 22
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 18
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 17
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 12
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 9
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 229960002887 deanol Drugs 0.000 description 9
- 239000012972 dimethylethanolamine Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 8
- 229940102253 isopropanolamine Drugs 0.000 description 8
- 229940011051 isopropyl acetate Drugs 0.000 description 8
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 8
- 239000011269 tar Substances 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 6
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 3
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 3
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 3
- KOVQQOMROOKART-UHFFFAOYSA-N 2-[2-hydroxyethyl(methyl)amino]propan-1-ol Chemical compound OCC(C)N(C)CCO KOVQQOMROOKART-UHFFFAOYSA-N 0.000 description 3
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 description 3
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 3
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 3
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 3
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 3
- 229940043276 diisopropanolamine Drugs 0.000 description 3
- 229940117955 isoamyl acetate Drugs 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- CDSLHOULXDQDPN-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].C[NH+](C)CCO CDSLHOULXDQDPN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011287 low-temperature tar Substances 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/007—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from the tar industry
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating a mixture of crude phenol and organic amine, which comprises the following steps: adding water and an organic solvent in the process of separating the crude phenol containing the organic amine by adopting an acidification and water washing method so as to obtain a phenol phase containing the organic solvent and a water phase containing an organic amine acidification water solution; rectifying the phenol phase containing the organic solvent to obtain crude phenol; and (3) rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine. The method can separate the crude phenol and the organic amine quickly and thoroughly, and has the advantages of simple separation process, continuous or intermittent separation, easy amplification, easy industrial implementation, low production cost and the like.
Description
Technical Field
The invention relates to the technical field of separation of phenol extracted by a phenol oil extraction method, in particular to a separation method of a mixture of crude phenol and organic amine.
Background
The raw material phenol oil is selected from phenol oil of high, medium and low temperature coal tar, direct coal liquefaction, indirect coal liquefaction, and fractions with the temperature of 170-230 ℃ or wider cut from various raw oil, generally called phenol oil, wherein the main components comprise phenols, neutral oil, some nitrogen-containing compounds and the like. The phenols mainly include phenol, o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, etc. The phenol extracted from the phenol oil, i.e. crude phenol, is a valuable chemical raw material, and the high-purity phenol product has wide application in the aspects of medicines, dyes, engineering plastics, fine chemicals and the like.
The traditional dephenolizing method is an acid-base method, and the process is simple, high in separation efficiency and good in crude phenol quality, so that the method is most widely applied to industry. However, the process consumes a large amount of strong acid and strong base, has high production cost, generates a large amount of phenol-containing wastewater, causes serious pollution to the environment, cannot meet the requirements of green chemical industry and environmental protection technology, and is gradually eliminated.
At present, extraction methods are mostly adopted for extracting crude phenol in the phenol oil, and the extraction effect is good. However, organic amine extractants are commonly used in the extraction process, and the organic amine extractants are often crossed with the boiling point of the main component of the crude phenol or form an azeotrope with the main component of the crude phenol, so that the organic amine extractants and the crude phenol cannot be separated and regenerated by the traditional methods such as rectification and the like.
Chinese patents CN106986750B and CN109825322A propose that after mixing and extracting an organic amine aqueous solution and phenol oil, a mixture of crude phenol and organic amine is obtained, and after acidifying and washing with an acidifying agent, the organic amine and crude phenol are separated and the organic amine is recovered. However, in practice, the simple acidic water washing is difficult to completely separate and recover the organic amines in the crude phenol, and the content of the organic amines in the crude phenol can only be reduced to 0.5% after many times of acidic water washing. This is far from enough because the existing national standard GB/T3711-; the default industry standard is more demanding, such as the need to ensure that the neutral oil in the crude phenol is below 0.5%. In the crude phenol obtained by the extraction method, the solvent also belongs to neutral oil, and the quality of the crude phenol is unqualified as long as the crude phenol contains other impurities slightly. On the other hand, the simple regeneration needs repeated acidification and water washing, so that not only is the crude phenol dissolved in water to cause loss, but also the water obtained after the water washing needs to be regenerated and recovered by a rectification method, a large amount of energy is consumed, the production process is long, the cost is high, and the industrial significance is not realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for separating the mixture of the crude phenol and the organic amine, which can quickly and thoroughly separate the crude phenol from the organic amine, solves the problems that the prior method for separating the crude phenol from the organic amine needs repeated water washing, the water consumption is overlarge, a large amount of energy is needed when water is recovered, the production cost is very high, the number of equipment units is too large, the residual quantity of the organic amine in the crude phenol is high, and the like, and has the advantages of simple separation process, continuity or intermittence, easy amplification, easy industrial implementation, low production cost and the like.
The purpose of the invention is realized by the following technical scheme:
a process for the separation of a mixture of crude phenol and organic amine comprising the steps of:
step 1, adding water and an organic solvent in the process of separating crude phenol containing organic amine by adopting an acidification water washing method, thereby obtaining a phenol phase containing the organic solvent and a water phase containing an organic amine acidification water solution;
step 2, rectifying the phenol phase containing the organic solvent to obtain crude phenol;
and 3, rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine.
Preferably, the adding water and the organic solvent in the process of separating the crude phenol containing the organic amine by using the acidification water washing method comprises the following steps:
mixing water, an organic solvent and crude phenol containing organic amine together, introducing an acidifying agent for acidification treatment, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing an organic amine acidified water solution;
or,
respectively introducing water, an organic solvent and crude phenol containing organic amine into an acidifying agent for acidification treatment, then mixing the water, the organic solvent and the crude phenol containing organic amine together, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing an organic amine acidified aqueous solution;
or,
acidifying water by introducing an acidifying agent into the water to obtain acidified water; introducing an acidifying agent into the crude phenol containing the organic amine for acidification treatment, thereby obtaining the acidified crude phenol containing the organic amine; and adding the acidified water, the organic solvent and the acidified crude phenol containing the organic amine into multistage countercurrent extraction equipment, and performing multistage countercurrent extraction and separation to obtain a phenol phase containing the organic solvent and a water phase containing the acidified aqueous solution of the organic amine.
Preferably, the mass ratio of the crude phenol containing organic amine to water is 1: 0.1-1: 2, and the mass ratio of the crude phenol containing organic amine to the organic solvent is 1: 0.1-1: 2.
Preferably, the acidifying agent is carbon dioxide or sulfur dioxide with the volume concentration of 10-100%, and the impurity component is at least one of water vapor, nitrogen and rare gas.
Preferably, water, an organic solvent and crude phenol containing organic amine are mixed together, an acidifying agent is introduced, the mixture is mixed and stirred for 0.1-2 hours at the temperature of 20-80 ℃, then the mixture is stood for layering for 0.1-2 hours, and a phenol phase containing the organic solvent and a water phase containing the acidified water solution of organic amine are obtained through separation.
Preferably, the acidified water is added into the multistage countercurrent extraction equipment from the 1 st stage, the organic solvent is added into the multistage countercurrent extraction equipment from the 1 st last stage, the acidified crude phenol containing the organic amine is added into the multistage countercurrent extraction equipment from the 2 nd last stage or together with the organic solvent, and the extraction separation is completed by countercurrent contact.
Preferably, when the content of the organic amine in the organic solvent-containing phenol phase is more than 0.1 wt%, the organic solvent-containing phenol phase is washed with water at least once until the content of the organic amine in the organic solvent-containing phenol phase is below 0.1 wt%; the step of washing the phenol phase containing the organic solvent by water is to mix water with the phenol phase containing the organic solvent, introduce an acidifying agent for acidification treatment, then stand for layering, and separate to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution; or, the step of washing the phenol phase containing the organic solvent by water is to respectively introduce acidulants into water and the phenol phase containing the organic solvent for acidification treatment, then mix the water and the phenol phase together, then stand the mixture for layering, and separate the mixture to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution.
Preferably, the mass ratio of the organic solvent-containing phenol phase to water is 1: 0.1-1: 2.
Preferably, the crude phenol containing organic amine is a heavy phase obtained when the phenol oil is extracted, and the content of organic amine is 10-80 wt%; wherein the organic amine is at least one of C2-C6 alcohol amine and dihydric alcohol amine.
Preferably, the organic solvent is at least one of alcohols of C4-C8, aromatic hydrocarbons of C6-C9, acetates and ethers.
According to the technical scheme provided by the invention, in the process of separating the crude phenol containing the organic amine by adopting an acidification washing method, water and an organic solvent are added to dissolve the crude phenol into the organic solvent, and the organic amine is mainly dissolved in the water after being acidified and is basically insoluble in the organic solvent, so that the phenol phase containing the organic solvent and the water phase containing an organic amine acidification water solution can be quickly and thoroughly separated, and the problems that the existing crude phenol and organic amine separation method needs repeated washing, the water consumption is overlarge, a large amount of energy consumption is needed when water is recovered, the production cost is very high, equipment units are too many, the organic amine residual quantity in the crude phenol is high and the like are solved.
Detailed Description
The technical solutions in the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The process for separating a mixture of crude phenol and organic amine provided by the present invention is described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
Method for separating mixture of crude phenol and organic amine
A process for separating a mixture of crude phenol and organic amine may include the steps of:
and A1, mixing water, an organic solvent and crude phenol containing organic amine together, introducing an acidifying agent for acidification treatment, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing an acidified aqueous solution of organic amine.
And A2, when the content of the organic amine in the organic solvent-containing phenol phase is more than 0.1 wt%, washing the organic solvent-containing phenol phase with water at least once until the content of the organic amine in the organic solvent-containing phenol phase is less than 0.1 wt%.
Step A3, rectifying the phenol phase containing the organic solvent to obtain crude phenol.
And A4, rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine.
Specifically, the method for separating the crude phenol and organic amine mixture may include the following embodiments:
(1) the crude phenol containing organic amine is a mixture of crude phenol and organic amine obtained after phenol oil solvent extraction dephenolization. The crude phenol containing organic amine is a heavy phase obtained when the phenol oil is extracted; for example: the organic amine-containing crude phenol can be a heavy phase obtained by extracting fractions of 170-230 ℃ or wider cut from high, medium and low temperature coal tar, phenol oil, direct coal liquefaction products, indirect coal liquefaction products and various raw oil. The content of the organic amine in the crude phenol containing the organic amine is 10-80 wt%. The organic amine is at least one of C2-C6 alcohol amine and dihydric alcohol amine; the alcamines of C2-C6 comprise ethanolamine, diethanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, dimethyldiethanolamine, propanolamine, isopropanolamine, dipropanolamine and diisopropanolamine; the dihydric alcohol amine comprises ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 2-butanediamine, 1, 3-butanediamine and 1, 4-butanediamine.
(2) The organic solvent can adopt at least one of C4-C8 alcohol, C6-C9 aromatic hydrocarbon, acetate and ether. The alcohols of C4-C8 comprise n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, n-heptyl alcohol, isoheptyl alcohol, sec-heptyl alcohol, isooctyl alcohol, sec-octyl alcohol, cyclohexanol, cycloheptyl alcohol and the like; the aromatic hydrocarbons of C6-C9 comprise toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, isopropylbenzene and the like; the acetate comprises n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate and the like; the ethers include isopropyl ether, propyl ether, butyl ether, isobutyl ether, sec-butyl ether, n-pentyl ether, isopentyl ether, ethylpropyl ether, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and the like.
(3) The acidifying agent is carbon dioxide or sulfur dioxide with the volume concentration of 10-100%, and the impurity component is at least one of water vapor, nitrogen and rare gas.
(4) The organic amine-containing crude phenol and water are mixed according to the mass ratio of 1: 0.1-1: 2, and the organic amine-containing crude phenol and an organic solvent are mixed according to the mass ratio of 1: 0.1-1: 2.
(5) In the step A1, mixing water, an organic solvent and crude phenol containing organic amine together, introducing an acidifying agent, mixing and stirring for 0.1-2 hours at 20-80 ℃, standing for layering for 0.1-2 hours, wherein the upper layer is a phenol phase containing the organic solvent, the lower layer is a water phase containing an acidified aqueous solution of organic amine, and separating to obtain the phenol phase containing the organic solvent and the water phase containing the acidified aqueous solution of organic amine.
(6) In step A2, the number of washing times of the organic solvent-containing phenol phase is 1 to 4. Firstly, the water washing of the phenol phase containing the organic solvent is to mix water and the phenol phase containing the organic solvent, introduce an acidifying agent for acidification treatment, then stand for layering, and separate to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution. Specifically, the organic solvent-containing phenol phase is washed by mixing water and the organic solvent-containing phenol phase according to the mass ratio of 1: 0.1-1: 2, introducing an acidifying agent, mixing and stirring at 20-80 ℃ for 0.1-2 hours, standing for layering for 0.1-2 hours, separating to obtain the organic solvent-containing phenol phase and the organic amine-containing acidified aqueous phase. Or the step of washing the phenol phase containing the organic solvent by water is to respectively introduce acidulants into water and the phenol phase containing the organic solvent for acidification treatment, then mix the water and the phenol phase together, then stand the mixture for layering, and separate the mixture to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution. Specifically, the mass ratio of the organic solvent-containing phenol phase to water is 1: 0.1-1: 2.
(7) In the step A3, a rectification tower is adopted to rectify the phenol phase containing the organic solvent, and the organic solvent and a small amount of water which can be recycled are recovered from the tower top; obtaining a crude phenol product without water, organic solvent and organic amine from the bottom of the tower; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure). In practical applications, it is preferred to obtain crude phenol by rectifying the phenol phase containing the organic solvent and having an organic amine content of 0.1 wt% or less.
(8) In step a4, the aqueous phase containing the acidified aqueous solution of the organic amine is rectified by a rectifying tower, water and a small amount of organic solvent are extracted from the top of the tower, and the regenerated organic amine is obtained from the bottom of the tower. The acidifying agent, water, organic solvent and organic amine can be recycled; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure).
(9) Step A3 is not sequenced with step A4, and can be run in parallel.
(II) separation method of crude phenol and organic amine mixture
A process for separating a mixture of crude phenol and organic amine may include the steps of:
and step B1, respectively introducing water, the organic solvent and the crude phenol containing the organic amine into an acidifying agent for acidification treatment, then mixing the water, the organic solvent and the crude phenol containing the organic amine together, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing the acidified water solution of the organic amine.
And B2, when the content of the organic amine in the organic solvent-containing phenol phase is more than 0.1 wt%, washing the organic solvent-containing phenol phase with water at least once until the content of the organic amine in the organic solvent-containing phenol phase is less than 0.1 wt%.
And step B3, rectifying the phenol phase containing the organic solvent to obtain crude phenol.
And B4, rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine.
Specifically, the method for separating the crude phenol and organic amine mixture may include the following embodiments:
(1) the crude phenol containing organic amine is a mixture of crude phenol and organic amine obtained after phenol oil solvent extraction dephenolization. The crude phenol containing organic amine is a heavy phase obtained when the phenol oil is extracted; for example: the organic amine-containing crude phenol can be a heavy phase obtained by extracting fractions of 170-230 ℃ or wider cut from high, medium and low temperature coal tar, phenol oil, direct coal liquefaction products, indirect coal liquefaction products and various raw oil. The content of the organic amine in the crude phenol containing the organic amine is 10-80 wt%. The organic amine is at least one of C2-C6 alcohol amine and dihydric alcohol amine; the alcamines of C2-C6 comprise ethanolamine, diethanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, dimethyldiethanolamine, propanolamine, isopropanolamine, dipropanolamine and diisopropanolamine; the dihydric alcohol amine comprises ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 2-butanediamine, 1, 3-butanediamine and 1, 4-butanediamine.
(2) The organic solvent can adopt at least one of C4-C8 alcohol, C6-C9 aromatic hydrocarbon, acetate and ether. The alcohols of C4-C8 comprise n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, n-heptyl alcohol, isoheptyl alcohol, sec-heptyl alcohol, isooctyl alcohol, sec-octyl alcohol, cyclohexanol, cycloheptyl alcohol and the like; the aromatic hydrocarbons of C6-C9 comprise toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, isopropylbenzene and the like; the acetate comprises n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate and the like; the ethers include isopropyl ether, propyl ether, butyl ether, isobutyl ether, sec-butyl ether, n-pentyl ether, isopentyl ether, ethylpropyl ether, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and the like.
(3) The acidifying agent is carbon dioxide or sulfur dioxide with the volume concentration of 10-100%, and the impurity component is at least one of water vapor, nitrogen and rare gas.
(4) The mass ratio of the organic amine-containing crude phenol to water is 1: 0.1-1: 2, and the mass ratio of the organic amine-containing crude phenol to the organic solvent is 1: 0.1-1: 2.
(5) And in the step B1, respectively introducing an acidifying agent into water, an organic solvent and crude phenol containing organic amine, mixing and stirring for 0.1-2 hours at the temperature of 20-80 ℃, then mixing together, standing for layering for 0.1-2 hours, separating to obtain a phenol phase containing the organic solvent and a water phase containing the organic amine acidified aqueous solution, wherein the upper layer is a phenol phase containing the organic solvent and the lower layer is a water phase containing the organic amine acidified aqueous solution.
(6) In step B2, the number of times of washing the organic solvent-containing phenol phase with water is 1 to 4. Firstly, the water washing of the phenol phase containing the organic solvent is to mix water and the phenol phase containing the organic solvent, introduce an acidifying agent for acidification treatment, then stand for layering, and separate to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution. Specifically, the organic solvent-containing phenol phase is washed by mixing water and the organic solvent-containing phenol phase according to the mass ratio of 1: 0.1-1: 2, introducing an acidifying agent, mixing and stirring at 20-80 ℃ for 0.1-2 hours, standing for layering for 0.1-2 hours, separating to obtain the organic solvent-containing phenol phase and the organic amine-containing acidified aqueous phase. Or the step of washing the phenol phase containing the organic solvent by water is to respectively introduce acidulants into water and the phenol phase containing the organic solvent for acidification treatment, then mix the water and the phenol phase together, then stand the mixture for layering, and separate the mixture to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution. Specifically, the mass ratio of the organic solvent-containing phenol phase to water is 1: 0.1-1: 2.
(7) In the step B3, a rectification tower is adopted to rectify the phenol phase containing the organic solvent, and the organic solvent and a small amount of water which can be recycled are recovered from the tower top; obtaining a crude phenol product without water, organic solvent and organic amine from the bottom of the tower; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure). In practical applications, it is preferred to obtain crude phenol by rectifying the phenol phase containing the organic solvent and having an organic amine content of 0.1 wt% or less.
(8) In step B4, the aqueous phase containing the acidified aqueous solution of the organic amine is rectified by a rectifying tower, water and a small amount of organic solvent are extracted from the top of the tower, and the regenerated organic amine is obtained from the bottom of the tower. The acidifying agent, water, organic solvent and organic amine can be recycled; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure).
(9) The step B3 and the step B4 have no sequence and can be operated in parallel.
(III) separation method of crude phenol and organic amine mixture
A process for separating a mixture of crude phenol and organic amine may include the steps of:
step C1, acidifying the water by introducing an acidifying agent to obtain acidified water; introducing an acidifying agent into the crude phenol containing the organic amine for acidification treatment, thereby obtaining the acidified crude phenol containing the organic amine; and (2) taking acidified water as a heavy phase and an organic solvent as a light phase, adding the acidified water, the organic solvent and the acidified crude phenol containing organic amine into multistage countercurrent extraction equipment, and performing multistage countercurrent extraction and separation to obtain a phenol phase containing the organic solvent and a water phase containing the acidified aqueous solution of organic amine.
And C2, rectifying the phenol phase containing the organic solvent to obtain crude phenol.
And step C3, rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine.
Specifically, the method for separating the crude phenol and organic amine mixture may include the following embodiments:
(1) the crude phenol containing organic amine is a mixture of crude phenol and organic amine obtained after phenol oil solvent extraction dephenolization. The crude phenol containing organic amine is a heavy phase obtained when the phenol oil is extracted; for example: the organic amine-containing crude phenol can be a heavy phase obtained by extracting fractions of 170-230 ℃ or wider cut from high, medium and low temperature coal tar, phenol oil, direct coal liquefaction products, indirect coal liquefaction products and various raw oil. The content of the organic amine in the crude phenol containing the organic amine is 10-80 wt%. The organic amine is at least one of C2-C6 alcohol amine and dihydric alcohol amine; the alcamines of C2-C6 comprise ethanolamine, diethanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, dimethyldiethanolamine, propanolamine, isopropanolamine, dipropanolamine and diisopropanolamine; the dihydric alcohol amine comprises ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 2-butanediamine, 1, 3-butanediamine and 1, 4-butanediamine.
(2) The organic solvent can adopt at least one of C4-C8 alcohol, C6-C9 aromatic hydrocarbon, acetate and ether. The alcohols of C4-C8 comprise n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, n-heptyl alcohol, isoheptyl alcohol, sec-heptyl alcohol, isooctyl alcohol, sec-octyl alcohol, cyclohexanol, cycloheptyl alcohol and the like; the aromatic hydrocarbons of C6-C9 comprise toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, isopropylbenzene and the like; the acetate comprises n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate and the like; the ethers include isopropyl ether, propyl ether, butyl ether, isobutyl ether, sec-butyl ether, n-pentyl ether, isopentyl ether, ethylpropyl ether, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and the like.
(3) The acidifying agent is carbon dioxide or sulfur dioxide with the volume concentration of 10-100%, and the impurity component is at least one of water vapor, nitrogen and rare gas.
(4) The mass ratio of the organic amine-containing crude phenol to water is 1: 0.1-1: 2, and the mass ratio of the organic amine-containing crude phenol to the organic solvent is 1: 0.1-1: 2.
(5) In step C1, acidifying water by adding an acidifying agent to the water to obtain acidified water; introducing an acidifying agent into the crude phenol containing the organic amine for acidification treatment, thereby obtaining the acidified crude phenol containing the organic amine; adding acidified water as a heavy phase and an organic solvent as a light phase into multistage countercurrent extraction equipment, adding the acidified water, the organic solvent and acidified crude phenol containing organic amine into the multistage countercurrent extraction equipment, adding the acidified crude phenol containing organic amine from a certain middle stage of the multistage countercurrent extraction equipment, and performing multistage countercurrent extraction separation, wherein the extraction stages are 3-10 stages, so as to obtain a phenol phase containing the organic solvent and a water phase containing an acidified aqueous solution of organic amine. And if the acidified water is added into the multistage countercurrent extraction equipment from the 1 st stage, adding the organic solvent into the multistage countercurrent extraction equipment from the 1 st stage, adding the acidified crude phenol containing the organic amine into the multistage countercurrent extraction equipment from the 2 nd stage or adding the crude phenol containing the organic amine and the organic solvent into the multistage countercurrent extraction equipment together, and finishing extraction by countercurrent contact. The extraction equipment can adopt a centrifugal extractor, an extraction tower, a mixing and stirring tank and a mixing and clarifying tank. If the extraction apparatus employs an extraction column, the organic solvent is fed from the bottom of the column, acidified water is fed from the top of the column, and the acidified crude phenol containing the organic amine is fed from the bottom of the column together with the organic solvent, or fed at a stage above the inlet of the organic solvent.
(6) In the step C2, a rectification tower is adopted to rectify the phenol phase containing the organic solvent, and the organic solvent and a small amount of water which can be recycled are recovered from the tower top; obtaining a crude phenol product without water, organic solvent and organic amine from the bottom of the tower; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure). In practical applications, it is preferred to obtain crude phenol by rectifying the phenol phase containing the organic solvent and having an organic amine content of 0.1 wt% or less.
(7) In step C3, the aqueous phase containing the acidified aqueous solution of the organic amine is rectified by a rectifying tower, water and a small amount of organic solvent are extracted from the top of the tower, and the regenerated organic amine is obtained from the bottom of the tower. The acidifying agent, water, organic solvent and organic amine can be recycled; the number of theoretical plates of the rectifying tower is 5-40, and the operating pressure can be 10-150 kPa (absolute pressure).
(8) The step C2 and the step C3 have no sequence and can be operated in parallel.
(IV) advantages of the invention
Compared with the prior art, the invention has at least the following advantages:
(1) in the invention, in the separation process of the crude phenol and the organic amine, the organic solvent is properly added, so that the crude phenol is dissolved in the organic solvent, and the organic amine is a water-soluble organic matter, is mainly dissolved in water after being acidified and is basically insoluble in the organic solvent, so that the organic amine and the crude phenol can be well separated.
(2) Because the organic solvent has low viscosity and good fluidity, the organic solvent phase in which the crude phenol is dissolved and the aqueous phase in which the organic amine is dissolved can quickly and thoroughly realize layering, the organic amine is prevented from being carried in the crude phenol, and the crude phenol is also prevented from being carried in the organic amine, so that the separation effect is obviously improved, the standing time required by the separation process is reduced, and the separation process is easy to amplify, operate and realize continuity.
(3) For the reasons, the washing times, the equipment unit number, the equipment investment, the total water consumption and the energy consumption required by water recovery are greatly reduced in the separation of the crude phenol and the organic amine, so that the production cost is obviously reduced.
(4) The method for separating the mixture of the crude phenol and the organic amine provided by the invention has the advantages that the content of the organic amine in the crude phenol can be easily controlled to be below 0.1 wt%, the contents of neutral oil and pyridine alkali in the crude phenol are obviously reduced, the technical index of reducing the content of the organic amine in the crude phenol to 0.5% in the prior art is obviously superior, the loss of an extracting agent is reduced, and the production cost is further reduced.
(5) According to the separation method of the mixture of the crude phenol and the organic amine, provided by the invention, the organic amine and the water are separated by adopting a rectification method, so that the separation effect of the organic amine, the water and the acidifying agent is obviously improved, the organic amine can be fully regenerated and recycled, the best extraction effect can be exerted, and the energy consumption in the production process is obviously reduced.
In conclusion, the embodiment of the invention can separate the crude phenol and the organic amine rapidly and thoroughly, solves the problems of repeated washing, excessive water consumption, large energy consumption during water recovery, high production cost, excessive equipment units, high organic amine residual quantity in the crude phenol and the like in the conventional crude phenol and organic amine separation method, and has the advantages of simple separation process, continuous or intermittent separation, easy amplification, easy industrial implementation, low production cost and the like.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the following detailed description is provided for the separation method of the crude phenol and organic amine mixture provided by the embodiment of the present invention with specific examples.
Example 1
A separation method of a mixture of crude phenol and organic amine is used for treating crude phenol (40% of diethanolamine) containing organic amine obtained by extracting a phenol oil fraction (distillation range is 170-230 ℃) from medium-temperature tar, and comprises the following steps:
step a1, simultaneously adding 1000kg of crude phenol containing organic amine, 1200kg of water and 800kg of organic solvent xylene (each 1/3 of o-xylene, m-xylene and p-xylene) into a stirring reaction kettle for mixing and stirring, and simultaneously introducing 60 percent of CO into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.2h at 65 ℃, then the mixture is kept stand for layering and separated to obtain a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without diethanolamine and xylene) and a water phase containing an organic amine acidified aqueous solution (namely, a diethanolamine aqueous solution).
Step a2, carrying out primary water washing on the phenol phase containing the organic solvent; adding the phenol phase containing the organic solvent obtained in the step a1 and 1200kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 60 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), so that the gas and the liquid are fully contacted and reactedMixing and stirring at 65 ℃ for 1.2h, standing for layering, and separating to obtain a phenol phase containing an organic solvent (namely a mixed solution of crude phenol without diethanolamine and xylene) and an aqueous phase containing an acidified aqueous solution of organic amine (namely an aqueous solution of diethanolamine).
Step a3, adding the phenol phase containing the organic solvent obtained in the step a2 into a 25-plate rectifying tower with the pressure of 50kPa for rectification, and obtaining the organic solvent xylene and a small amount of water at the tower top, wherein the organic solvent xylene and the small amount of water can be recycled; and obtaining a crude phenol product without organic solvent, diethanolamine and water at the bottom of the tower, wherein the content of the diethanolamine is 0.02 percent.
Step a4, pumping the water phase containing the organic amine acidified water solution obtained in the step a1 and the water phase containing the organic amine acidified water solution obtained in the step a2 into a 25-plate rectifying tower with the pressure of 50kPa for rectification, and collecting CO at the top of the tower2Gas, water and a small amount of dimethylbenzene can be recycled; the regenerated diethanolamine is obtained from the tower bottom, wherein the phenol content is 1.3%, and the diethanolamine can be recycled.
Specifically, the main process parameters of example 1 of the present invention are shown in table 1 below:
TABLE 1
Example 2
A separation method of a mixture of crude phenol and organic amine is used for treating crude phenol (containing 60% of 1, 2-propane diamine) containing organic amine obtained by extracting a phenol oil fraction (130-280 ℃) from low-temperature tar, and comprises the following steps:
step b1, adding 1000kg of the crude phenol containing organic amine, 2000kg of water and 500kg of organic solvent (sec-octanol: isooctanol: 2:3) into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 80% into the bottom of the reaction kettle at the same time2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 70 ℃, then the mixture is kept stand for layering and separated to obtain a phenol phase containing an organic solvent (namely a mixed solution of crude phenol without 1, 2-propane diamine and the organic solvent) and an organic amine acidified aqueous solutionThe aqueous phase (i.e., aqueous 1, 2-propanediamine solution).
B2, carrying out primary water washing on the phenol phase containing the organic solvent; adding the phenol phase containing the organic solvent obtained in the step b1 and 2000kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 80 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 70 ℃, then the mixture is kept stand for layering and separated to obtain a phenol phase containing an organic solvent (namely a mixed solution of crude phenol without 1, 2-propane diamine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely a1, 2-propane diamine aqueous solution).
B3, adding the phenol phase containing the organic solvent obtained in the step b2 into a rectifying tower with the pressure of 110kPa and 40 plates for rectifying, and obtaining the organic solvent and a small amount of water at the top of the tower, wherein the organic solvent and the small amount of water can be recycled; the crude phenol product without organic solvent, 1, 2-propane diamine and water is obtained at the bottom of the tower, wherein the content of the 1, 2-propane diamine is 0.08 percent.
Step b4, pumping the water phase containing the organic amine acidified water solution obtained in the step b1 and the water phase containing the organic amine acidified water solution obtained in the step b2 into a rectifying tower with the pressure of 110kPa and 40 plates for rectifying, and collecting CO at the top of the tower2Gas, water and a small amount of organic solvent can be recycled; the regenerated 1, 2-propane diamine is obtained from the tower bottom, wherein the content of phenol is 2.5 percent, and the regenerated 1, 2-propane diamine can be recycled.
Specifically, the main process parameters of example 2 of the present invention are shown in table 2 below:
TABLE 2
Example 3
A method for separating a mixture of crude phenol and organic amine is used for processing crude phenol (containing 70% of ethanolamine and ethylenediamine, which are abbreviated as mixed amine in the embodiment) containing organic amine obtained from medium-temperature tar extraction, and comprises the following steps:
step c1, 1000kg of the crude phenol containing organic amine, 1200kg of water, 300kg of organic solvent (isopropyl ether: propyl ether)Ether 1:1) is added into a stirring reaction kettle at the same time, mixed and stirred, and CO with the content of 90 percent is introduced into the bottom of the reaction kettle at the same time2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 55 ℃, then the mixture is kept stand for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without mixed amine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a mixed amine solution) are obtained through separation.
Step c2, carrying out first water washing on the phenol phase containing the organic solvent; adding the phenol phase containing the organic solvent obtained in the step c1 and 1200kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 90 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 55 ℃, then the mixture is kept stand for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without mixed amine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a mixed amine solution) are obtained through separation.
Step c3, carrying out secondary water washing on the phenol phase containing the organic solvent; adding the phenol phase containing the organic solvent obtained in the step c2 and 1200kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 90 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 55 ℃, then the mixture is kept stand for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without mixed amine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a mixed amine solution) are obtained through separation.
Step c4, adding the phenol phase containing the organic solvent obtained in the step c3 into a 25-plate rectifying tower with the pressure of 150kPa for rectification, and obtaining the organic solvent and a small amount of water at the top of the tower, wherein the organic solvent and the small amount of water can be recycled; the crude phenol product without organic solvent, mixed amine and water is obtained at the bottom of the tower, wherein the content of the mixed amine is 0.06 percent.
Step c5, pumping 25 blocks of the water phase containing the organic amine acidified water solution obtained in the step c1, the water phase containing the organic amine acidified water solution obtained in the step c2 and the water phase containing the organic amine acidified water solution obtained in the step c3 together with the water phase with the pressure of 150kPaRectifying in a rectifying tower of the plate to obtain CO at the top of the tower2Gas, water and a small amount of organic solvent can be recycled; the regenerated ethanolamine and ethylenediamine are obtained from the tower bottom, wherein the content of phenol is 3.5%, and the regenerated ethanolamine and ethylenediamine can be recycled.
Specifically, the main process parameters of example 3 of the present invention are shown in table 3 below:
TABLE 3
Example 4
A separation method of a mixture of crude phenol and organic amine is used for processing crude phenol (containing 60% of dimethylethanolamine) containing organic amine obtained from medium-temperature tar extraction, and comprises the following steps:
step d1, simultaneously adding 1000kg of the crude phenol containing the organic amine, 2000kg of water and 300kg of organic solvent (ethyl tert-butyl ether) into a stirring reaction kettle for mixing and stirring, and simultaneously introducing CO with the content of 80% into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 50 ℃, then the mixture is kept stand for layering, and the phenol phase containing the organic solvent (namely the mixed solution of the crude phenol without the dimethylethanolamine and the ethyl tert-butyl ether) and the water phase containing the organic amine acidified water solution (namely the dimethylethanolamine water solution) are obtained through separation.
D2, carrying out primary water washing on the phenol phase containing the organic solvent; adding the organic solvent-containing phenol phase obtained in the step d1 and 2000kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 80% into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 50 ℃, then the mixture is kept stand for layering, and the phenol phase containing the organic solvent (namely the mixed solution of the crude phenol without the dimethylethanolamine and the ethyl tert-butyl ether) and the water phase containing the organic amine acidified water solution (namely the dimethylethanolamine water solution) are obtained through separation.
D3, adding the phenol phase containing the organic solvent obtained in the step d2 into a rectifying tower with the pressure of 110kPa and 5 plates for rectifying, and obtaining the organic solvent ethyl tert-butyl ether and a small amount of water at the top of the tower, wherein the organic solvent ethyl tert-butyl ether and the small amount of water can be recycled; and obtaining a crude phenol product without organic solvent, dimethylethanolamine and water at the bottom of the tower, wherein the content of the dimethylethanolamine is 0.02 percent.
Step d4, pumping the water phase containing the organic amine acidified water solution obtained in the step d1 and the water phase containing the organic amine acidified water solution obtained in the step d2 into a rectifying tower with the pressure of 110kPa and 5 plates for rectifying, and collecting CO at the top of the tower2Gas, water and a small amount of organic solvent ethyl tert-butyl ether can be recycled; the regenerated dimethylethanolamine is obtained from the tower bottom, wherein the content of phenol is 1.5 percent and can be recycled.
Specifically, the main process parameters of example 4 of the present invention are shown in table 4 below:
TABLE 4
Example 5
A method for separating a mixture of crude phenol and organic amine, which is used for treating crude phenol (containing 5 percent of propanolamine and 5 percent of isopropanolamine and 10 percent of organic amine in total) containing organic amine obtained from medium-temperature tar extraction, comprises the following steps:
step e1, simultaneously adding 1000kg of the crude phenol containing organic amine, 500kg of water and 2000kg of organic solvent (n-heptanol) into a stirring reaction kettle for mixing and stirring, and simultaneously introducing CO with the content of 10% into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), so that gas and liquid are fully contacted and reacted, the mixture is stirred for 0.1h at the temperature of 35 ℃, then the mixture is stood for layering, and a phenol phase (namely, a mixed solution of crude phenol and n-heptanol from which propanolamine and isopropanolamine are removed) containing an organic solvent and a water phase (namely, aqueous solutions of propanolamine and isopropanolamine) containing an organic amine acidified water solution are obtained through separation.
Step e2, adding the phenol phase containing the organic solvent obtained in the step e1 into a rectifying tower with the pressure of 10kPa and 5 plates for rectifying, and obtaining the organic solvent n-heptanol and a small amount of water at the tower top, wherein the organic solvent n-heptanol and the small amount of water can be recycled; the crude phenol product without organic solvent, organic amine and water is obtained at the bottom of the tower, wherein the content of the organic amine is 0.07 percent.
Step e3, pumping the water phase containing the organic amine acidified water solution obtained in the step e1 into a rectifying tower with the pressure of 10kPa and 5 plates for rectifying, and collecting CO at the tower top2Gas, water and a small amount of organic solvent n-heptanol can be recycled; the regenerated propanolamine and isopropanolamine are obtained from the tower bottom, wherein the phenol content is 1.5%, and the regenerated propanolamine and isopropanolamine can be recycled.
Specifically, the main process parameters of example 5 of the present invention are shown in table 5 below:
TABLE 5
Example 6
A separation method of a mixture of crude phenol and organic amine is used for processing crude phenol (containing 20% of ethanolamine) containing organic amine obtained from medium-temperature tar extraction, and comprises the following steps:
step f1, use of 30% CO2Respectively acidifying the crude phenol containing the organic amine and water in a gas-liquid contact device to obtain acidified water and acidified crude phenol containing the organic amine; extraction was carried out in a 10-stage countercurrent extraction column, acidified water was added as a heavy phase from the 1 st stage (number of stages in the order from top to bottom) of the extraction column at a rate of 100kg/h, an organic solvent (n-butanol) was added as a light phase from the 10 th stage of the extraction column at a rate of 1500kg/h, and acidified crude phenol containing an organic amine was added from the 9 th stage of the extraction column at a rate of 1000 kg/h. The operating temperature of the extraction column was 50 ℃ and atmospheric pressure. After extraction is finished, a mixed solution (namely a phenol phase containing an organic solvent) of crude phenol and n-butanol from which the organic amine is removed is obtained at the top of the extraction tower, and an organic amine aqueous solution (namely a water phase containing an organic amine acidified aqueous solution) is obtained at the bottom of the extraction tower.
Step f2, adding the phenol phase containing the organic solvent obtained in the step f1 into a rectifying tower with the pressure of 10kPa and 5 plates for rectifying, and obtaining the organic solvent n-butanol and a small amount of water at the tower top, which can be recycled; the crude phenol product without organic solvent, ethanolamine and water is obtained at the bottom of the tower, wherein the ethanolamine content is 0.05 percent.
Step f3, pumping the water phase containing the organic amine acidified water solution obtained in the step f1 into a rectifying tower with the pressure of 10kPa and 5 plates for rectifying, and collecting CO at the tower top2Gas, water and a small amount of organic solvent n-butyl alcohol can be recycled; the regenerated ethanolamine is obtained from the tower bottom, wherein the content of phenol is 2.5 percent, and the ethanolamine can be recycled.
Specifically, the main process parameters of example 6 of the present invention are shown in table 6 below:
TABLE 6
Example 7
A method for separating a mixture of crude phenol and organic amine, which is used for processing crude phenol (containing 30% of methylethanolamine) containing organic amine obtained from medium-temperature tar extraction, comprises the following steps:
step g1, use of 60% SO2Respectively acidifying water and the crude phenol containing the organic amine in a gas-liquid contact device (wherein the impurity component is nitrogen), so as to obtain acidified water and the acidified crude phenol containing the organic amine; extraction is carried out in a 3-stage countercurrent extraction tower, acidified water is added as a heavy phase from the 1 st stage (the number of stages is from top to bottom) of the extraction tower at the rate of 900kg/h, an organic solvent (cumene) is added from the 3 rd stage of the extraction tower together with the acidified crude phenol containing the organic amine, the organic solvent (cumene) is added at the rate of 1000kg/h, and the acidified crude phenol containing the organic amine is added at the rate of 1000 kg/h. The operating temperature of the extraction tower is 20 ℃ and normal pressure. After extraction is finished, a mixed solution (namely a phenol phase containing an organic solvent) of crude phenol and isopropyl benzene from which the organic amine is removed is obtained at the top of the extraction tower, and an organic amine aqueous solution (namely a water phase containing an organic amine acidified aqueous solution) is obtained at the bottom of the extraction tower.
Step g2, adding the phenol phase containing the organic solvent obtained in the step g1 into a 25-plate rectifying tower with the pressure of 50kPa for rectification, and obtaining the organic solvents of cumene, methylethanolamine and a small amount of water at the tower top, wherein the organic solvents can be recycled; the crude phenol product without organic solvent, methylethanolamine and water is obtained at the bottom of the tower, wherein the content of the methylethanolamine is 0.08 percent.
Step g3, pumping the water phase containing the organic amine acidified water solution obtained in the step g1 into a 25-plate rectifying tower with the pressure of 50kPa for rectification, and collecting CO at the tower top2Gas, water and a small amount of organic solvent cumene can be recycled; the regenerated methylethanolamine is obtained from the tower bottom, wherein the content of phenol is 5%, and the regenerated methylethanolamine can be recycled.
Specifically, the main process parameters of example 7 of the present invention are shown in table 7 below:
TABLE 7
Example 8
A method for separating a mixture of crude phenol and organic amine, which is used for treating crude phenol (containing 50% of propanolamine) containing organic amine obtained from medium-temperature tar extraction, comprises the following steps:
step h1, simultaneously adding 1000kg of the crude phenol containing organic amine, 1000kg of water and 1200kg of organic solvent (isopropyl acetate) into a stirring reaction kettle for mixing and stirring, and simultaneously introducing 70% of CO at the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 75 ℃, then the mixture is kept stand for layering, and a phenol phase containing an organic solvent (namely a mixed solution of crude phenol without propanolamine and isopropyl acetate) and a water phase containing an organic amine acidified water solution (namely a propanolamine water solution) are obtained through separation.
H2, carrying out primary water washing on the phenol phase containing the organic solvent; adding the organic solvent-containing phenol phase obtained in the step h1 and 1000kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing 70 percent of CO at the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1.5h at the temperature of 75 ℃, then the mixture is kept stand for layering and separated to obtain a phenol phase containing an organic solvent (namely the mixed solution of crude phenol without propanolamine and isopropyl acetate) and an acidified aqueous solution containing organic amineThe aqueous phase of (i.e., aqueous propanolamine).
Step h3, adding the phenol phase containing the organic solvent obtained in the step h2 into a rectifying tower with the pressure of 50kPa and 40 plates for rectifying, and obtaining the organic solvent isopropyl acetate and a small amount of water at the tower top, which can be recycled; and obtaining a crude phenol product without organic solvent, propanolamine and water at the bottom of the tower, wherein the propanolamine content is 0.09%.
Step h4, pumping the water phase containing the organic amine acidified water solution obtained in the step h1 and the water phase containing the organic amine acidified water solution obtained in the step h2 into a rectifying tower with the pressure of 50kPa and 40 plates for rectifying, and collecting CO at the top of the tower2Gas, water and a small amount of organic solvent isopropyl acetate can be recycled; the regenerated propanolamine is obtained from the tower bottom, wherein the phenol content is 2.5 percent, and the propanolamine can be recycled.
Specifically, the main process parameters of example 8 of the present invention are shown in table 8 below:
TABLE 8
Example 9
A separation method of a mixture of crude phenol and organic amine is used for processing crude phenol (containing 30% of 1, 3-propane diamine) containing organic amine obtained from medium-temperature tar extraction, and comprises the following steps:
step I1, 1000kg of the organic amine-containing crude phenol, 300kg of water, 1600kg of organic solvent (butyl acetate: isobutyl acetate: 1) are added into a stirring reaction kettle simultaneously for mixing and stirring, and simultaneously, 50% of CO is introduced into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 65 ℃, then the mixture is stood for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without 1, 3-propane diamine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a1, 3-propane diamine aqueous solution) are obtained through separation.
Step I2, carrying out first water washing on a phenol phase containing an organic solvent; the organic solvent-containing phenol phase obtained in step I1 was mixed with 300kg of waterThen adding the mixture into a stirring reaction kettle for mixing and stirring, and simultaneously introducing CO with the content of 50 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 65 ℃, then the mixture is stood for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without 1, 3-propane diamine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a1, 3-propane diamine aqueous solution) are obtained through separation.
Step I3, carrying out secondary water washing on the phenol phase containing the organic solvent; adding the phenol phase containing the organic solvent obtained in the step I2 and 300kg of water into a stirring reaction kettle at the same time, mixing and stirring, and introducing CO with the content of 50 percent into the bottom of the reaction kettle2(the impurity components are water vapor and nitrogen), the gas and the liquid are fully contacted and reacted, the mixture is stirred for 1h at the temperature of 65 ℃, then the mixture is stood for layering, and a phenol phase containing an organic solvent (namely, a mixed solution of crude phenol without 1, 3-propane diamine and the organic solvent) and a water phase containing an organic amine acidified aqueous solution (namely, a1, 3-propane diamine aqueous solution) are obtained through separation.
Step I4, adding the phenol phase containing the organic solvent obtained in the step I3 into a rectifying tower with the pressure of 150kPa and 25 plates for rectifying, and obtaining the organic solvent and a small amount of water at the top of the tower, wherein the organic solvent and the small amount of water can be recycled; the crude phenol product without organic solvent, 1, 3-propane diamine and water is obtained at the bottom of the tower, wherein the content of the 1, 3-propane diamine is 0.1 percent.
Step I5, pumping the water phase containing the organic amine acidified water solution obtained in the step I1, the water phase containing the organic amine acidified water solution obtained in the step I2 and the water phase containing the organic amine acidified water solution obtained in the step I3 into a rectifying tower with pressure of 150kPa and 25 plates for rectifying, and collecting CO at the top of the tower2Gas, water and a small amount of organic solvent can be recycled; the regenerated 1, 3-propane diamine is obtained from the tower bottom, wherein the phenol content is 5%, and the regenerated 1, 3-propane diamine can be recycled.
Specifically, the main process parameters of example 9 of the present invention are shown in table 9 below:
TABLE 9
Comparative example 1
The same operation as in example 1 was carried out except that xylene as an organic solvent was not added, whereby the content of organic amine in the crude phenol product was 24.9%, and the content of phenol in the organic amine obtained by regeneration was 74.2%. It can be seen that the objective of separating the organic amine from the crude phenol is not achieved at all. If the organic amine in the crude phenol product is to be removed to below 0.1%, more than 6 times of water washing operation are needed.
Specifically, the main process parameters of comparative example 1 are shown in table 10 below:
watch 10
Comparative example 2
The same operation as in example 7 was carried out except that cumene as an organic solvent was not added, whereby the content of organic amine in the crude phenol product was 18.8% and the content of phenol in the organic amine obtained by regeneration was 67%.
Specifically, the main process parameters of comparative example 2 are shown in table 11 below:
TABLE 11
Data comparison
The raw materials, solvents, operating conditions and impurities in the products in examples 1 to 9 of the present invention and comparative examples 1 to 2 were summarized to obtain the following table 12:
TABLE 12
As can be seen from table 12: the products in the embodiments 1-9 of the invention all reach the expected standards.
In conclusion, the embodiment of the invention can separate the crude phenol and the organic amine rapidly and thoroughly, solves the problems of repeated washing, excessive water consumption, large energy consumption during water recovery, high production cost, excessive equipment units, high organic amine residual quantity in the crude phenol and the like in the conventional crude phenol and organic amine separation method, and has the advantages of simple separation process, continuous or intermittent separation, easy amplification, easy industrial implementation, low production cost and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for separating a mixture of crude phenol and organic amine, comprising the steps of:
step 1, adding water and an organic solvent in the process of separating crude phenol containing organic amine by adopting an acidification water washing method, thereby obtaining a phenol phase containing the organic solvent and a water phase containing an organic amine acidification water solution;
step 2, rectifying the phenol phase containing the organic solvent to obtain crude phenol;
and 3, rectifying the water phase containing the organic amine acidified water solution to obtain the organic amine.
2. The method of claim 1, wherein the adding water and organic solvent during the separating of the crude phenol containing organic amine by the acidified water wash comprises:
mixing water, an organic solvent and crude phenol containing organic amine together, introducing an acidifying agent for acidification treatment, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing an organic amine acidified water solution;
or,
respectively introducing water, an organic solvent and crude phenol containing organic amine into an acidifying agent for acidification treatment, then mixing the water, the organic solvent and the crude phenol containing organic amine together, standing for layering, and separating to obtain a phenol phase containing the organic solvent and a water phase containing an organic amine acidified aqueous solution;
or,
acidifying water by introducing an acidifying agent into the water to obtain acidified water; introducing an acidifying agent into the crude phenol containing the organic amine for acidification treatment, thereby obtaining the acidified crude phenol containing the organic amine; and adding the acidified water, the organic solvent and the acidified crude phenol containing the organic amine into multistage countercurrent extraction equipment, and performing multistage countercurrent extraction and separation to obtain a phenol phase containing the organic solvent and a water phase containing the acidified aqueous solution of the organic amine.
3. The method for separating the mixture of the crude phenol and the organic amine according to claim 2, wherein the mass ratio of the crude phenol containing the organic amine to the water is 1:0.1 to 1:2, and the mass ratio of the crude phenol containing the organic amine to the organic solvent is 1:0.1 to 1: 2.
4. The method for separating the mixture of crude phenol and organic amine according to claim 2, wherein the acidifying agent is carbon dioxide or sulfur dioxide with a volume concentration of 10-100%, and the impurity component is at least one of water vapor, nitrogen gas and rare gas.
5. The method for separating the mixture of the crude phenol and the organic amine according to claim 2, wherein the water, the organic solvent and the crude phenol containing the organic amine are mixed together, an acidulant is introduced, the mixture is mixed and stirred for 0.1 to 2 hours at the temperature of 20 to 80 ℃, then the mixture is kept still for layering, the standing and layering time is 0.1 to 2 hours, and the phenol phase containing the organic solvent and the water phase containing the acidified aqueous solution of the organic amine are separated.
6. The method for separating a mixture of crude phenol and organic amine according to claim 2, wherein the acidified water is fed from the 1 st stage to a multistage countercurrent extraction apparatus, the organic solvent is fed from the 1 st stage to the multistage countercurrent extraction apparatus, the acidified crude phenol containing organic amine is fed from the 2 nd stage or together with the organic solvent to the multistage countercurrent extraction apparatus, and the extraction separation is completed by countercurrent contact.
7. The process according to any one of claims 1 to 6, wherein when the organic amine content in the organic solvent-containing phenol phase is greater than 0.1 wt%, the organic solvent-containing phenol phase is washed with water at least once until the organic amine content in the organic solvent-containing phenol phase is below 0.1 wt%;
the step of washing the phenol phase containing the organic solvent by water is to mix water with the phenol phase containing the organic solvent, introduce an acidifying agent for acidification treatment, then stand for layering, and separate to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution; or, the step of washing the phenol phase containing the organic solvent by water is to respectively introduce acidulants into water and the phenol phase containing the organic solvent for acidification treatment, then mix the water and the phenol phase together, then stand the mixture for layering, and separate the mixture to obtain the phenol phase containing the organic solvent and the water phase containing the organic amine acidified water solution.
8. The method for separating a mixture of crude phenol and organic amine according to claim 7, wherein the mass ratio of the organic solvent-containing phenol phase to water is 1:0.1 to 1: 2.
9. The method for separating a mixture of crude phenol and organic amine according to any one of claims 1 to 6, wherein the crude phenol containing organic amine is a heavy phase obtained when phenol oil is extracted, and the content of organic amine is 10-80 wt%; wherein the organic amine is at least one of C2-C6 alcohol amine and dihydric alcohol amine.
10. The method for separating a mixture of crude phenol and organic amine according to any one of claims 1 to 6, wherein the organic solvent is at least one of C4-C8 alcohol, C6-C9 aromatic hydrocarbon, acetate, and ether.
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